Journal
CHEMICAL SCIENCE
Volume 13, Issue 46, Pages 13732-13740Publisher
ROYAL SOC CHEMISTRY
DOI: 10.1039/d2sc04613j
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Funding
- Monash University
- Australian Research Council [FT180100610]
- Australian Research Council for the ARC Centre of Excellence for Enabling Eco-Efficient Bene.ciation of Minerals [CE200100009]
- CNRS
- Universite de Strasbourg
- ARC Discovery scheme [ARC DP180101187]
- Australian government for a Research Training Program (RTP) scholarship
- Australian Research Council [FT180100610] Funding Source: Australian Research Council
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The metastable trilacunary heteropolyoxomolybdate and ditopic pyridyl bearing diarylethene self-assemble to form a photo-active molecular capsule through a ligand replacement method. The spatial arrangement of the ligands is determined by the surface chemistry of the molecular metal oxide precursor. The study also discovers a photochemical cascade involving rapid photoinduced ring closure and electron transfer.
The metastable trilacunary heteropolyoxomolybdate [PMo9O31(py)(3)](3-) - {PMo9}; py = pyridine) and the ditopic pyridyl bearing diarylethene (DAE) (C25H16N2F6S2) self-assemble via a facile ligand replacement methodology to yield the photo-active molecular capsule [(PMo9O31)(2)(DAE)(3)](6-). The spatial arrangement and conformation of the three DAE ligands are directed by the surface chemistry of the molecular metal oxide precursor with exclusive ligation of the photo-active antiparallel rotamer to the polyoxometalate (POM) while the integrity of the assembly in solution has been verified by a suite of spectroscopic techniques. Electrocyclisation of the three DAEs occurs sequentially and has been investigated using a combination of steady-state and time-resolved spectroscopies with the discovery of a photochemical cascade whereby rapid photoinduced ring closure is followed by electron transfer from the ring-closed DAE to the POM in the latent donor-acceptor system on subsequent excitation. This interpretation is also supported by computational and detailed spectroelectrochemical analysis. Ring-closing quantum yields were also determined using a custom quantum yield determination setup (QYDS), providing insight into the impact of POM coordination on these processes.
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